Use of cationic layered materials, compositions, comprising these materials, and the preparation of cationic layered materials

ABSTRACT

Cationic layered materials, a process for their preparation and their use in hydrocarbon conversion, purification, and synthesis processes, such as fluid catalytic cracking. Cationic layered materials are especially suitable for the reduction of SOx and NOx emissions and the reduction of the sulfur and nitrogen content in fuels like gasoline and diesel. The new preparation process avoids the use of metal salts and does not require the formation of anionic clay as an intermediate.

CROSS REFERENCE TO RELATED APPLICATIONS

This application claims priority of U.S. Patent Application No.60/391,045, filed Jun. 25, 2002 and EP Patent Application No.02078429.4, filed Aug. 20, 2002.

BACKGROUND OF THE INVENTION

1. Field of the Invention

This invention relates to a new use of cationic layered materials,compositions comprising these materials, and a process for thepreparation of cationic layered materials.

2. Prior Art

A Cationic Layered Material (CLM) is a crystalline NH₄-Me(II)-TM-O phasewith a characteristic X-ray diffraction pattern. In this structure,Me(II) represents a divalent metal and TM stands for a transition metal.The structure of a CLM consists of negatively charged layers of divalentmetal octrahedra and transition metal tetrahedra withcharge-compensating cations sandwiched between these layers.

The CLM structure is related to that of hydrotalcite andhydrotalcite-like materials. These materials, also referred to by theskilled person as layered double hydroxides (LDH) or anionic clays, arebuilt up of Me(II)-Al hydroxide sheets with exchangeable anions in theinterlayers. Analogous to the term “anionic clay” being a synonym forhydrotalcites and hydrotalcite-like materials, “cationic clay” can beused as a synonym for CLM.

CLMs are known from the prior art. M. P. Astier et al. (Ann. Chim. Fr.Vol. 12, 1987, pp. 337–343) prepare CLMs by first dissolving ammoniumhepta molybdate and nickel nitrate in an aqueous ammonia solution andsubsequently altering the pH by evaporating ammonia, resulting inprecipitation. After aging, washing, and drying, pure crystalline CLMsare formed with a characteristic X-ray diffraction pattern.

A similar precipitation procedure is disclosed in U.S. Pat. No.6,156,695 for the preparation of CLMs containing Ni, W, and Mo.

D. Levin, S. Soled, and J. Ying (Chem. Mater. Vol. 8, 1996, pp.836–843;ACS Symp. Ser. Vol. 622, 1996, pp. 237–249; Stud. Surf, Sci. Catal. Vol.118, 1998, pp. 359–367) also disclose the preparation of CLMs. Theirprocess involves the steps of (a) precipitating a divalent metal saltand aluminium nitrate, (b) aging the precipitate to form an anionicclay, (c) calcining the anionic clay to form a mixed oxide, and (d)contacting and reacting the mixed oxide with ammoniumheptamolybdate—thereby removing aluminium ions and incorporatingmolybdate ions—resulting in a CLM with a trace amount, e.g. 0.63 wt %,of aluminium.

It has been found that CLMs can suitably be used in or as a catalyst orcatalyst additive in a hydrocarbon conversion, purification, orsynthesis process, particularly in the oil refining industry andFischer-Tropsch processes. Examples of processes where CLMs can suitablybe used are catalytic cracking, hydrogenation, dehydrogenation,hydrocracking, hydroprocessing (hydrodenitrogenation,hydrodesulfurization, hydrodemetallisation), polymerisation, steamreforming, base-catalysed reactions, Fischer-Tropsch, and the reductionof SOx and NOx emissions. They are especially suitable for use in FCCprocesses, particularly as active material in FCC catalysts or catalystadditives for (i) the reduction of the nitrogen and/or sulfur content offuels like gasoline and/or diesel and/or (ii) the reduction of SOxand/or NOx emissions.

SUMMARY OF THE INVENTION

In one embodiment, the present invention comprises a compositioncomprising a cationic layered material and 1–50 weight percent ofaluminium oxide, aluminium hydroxide, metal aluminate, or aluminiummolybdate.

In a second embodiment the present invention comprises a compositioncomprising a cationic layered material and a divalent metal compound.

In a third embodiment, the present invention comprises a compositioncomprising a cationic layered material and a transition metal compound.

In a fourth embodiment, the present invention comprises an FCC catalystcomposition comprising a cationic layered material.

In a fifth embodiment, the present invention comprises an FCC catalystadditive composition comprising a cationic layered material.

In a sixth embodiment the present invention comprises a processcomprising the steps of:

-   a) preparing a slurry comprising a water-insoluble aluminium source    and a divalent metal source,-   b) drying the slurry of step a) and calcining the dried material to    form a first calcined material,-   c) optionally rehydrating the product of step b) to obtain an    anionic clay, followed by calcining the anionic clay to form a    second calcined material,-   d) contacting a slurry of either the first or the second calcined    material with an ammonium transition metal salt,-   e) aging the resulting slurry.

In a seventh embodiment, the present invention comprises shaped bodiesobtained by the above processes.

In an eighth embodiment, the present invention comprises a process forthe conversion, purification, or synthesis of hydrocarbons whereinhydrocarbons are contacted with a cationic layered material athydrocarbon conversion, purification, or synthesis conditions.

Other embodiments of the present invention comprise details relating tocompositions, reaction ingredients and conditions, all of which are setforth hereinbelow.

BRIEF DESCRIPTION OF THE DRAWING

FIG. 1 displays the sulfur concentration in FCC gasoline versus thehydrocarbon conversion for different cationic layered materials and tworeference samples.

DETAILED DESCRIPTION OF THE INVENTION

The present invention relates to the use of a cationic layered materialin a hydrocarbon conversion, purification, or synthesis process. Thiscationic layered material may have been prepared according to theprocess of the invention described herein, or according to any otherprocess, e.g. the prior art processes mentioned above.

The prior art processes for preparing CLMs all use water-solubledivalent metal and aluminium salts as starting material, which isparticularly disadvantageous. First of all, these soluble metal saltsare relatively expensive. Second, they require a precipitation process,which is not very attractive to perform on an industrial scale, becauseit involves repeated filtering a washing steps of very fine (colloidaltype) particles. This involves large scale plant equipment, very lowthroughput capacities, and large volumes of contaminated waste water.Third, the use of salts implies the use of anions. These anions eitherhave to be removed by washing and filtering steps—incurring the abovefiltration problems with the fine-particled materials and waste waterstreams containing, e.g., nitrates, sulfates, halogens, etc.—or will beemitted as environmentally harmful gases like nitrogen oxides, halogens,sulfur oxides, etc. during the drying or calcination steps.

The present invention also provides a process for the production ofcationic layered materials using inexpensive raw materials. Inparticular, the use of metal salts is avoided, resulting in a processthat is particularly environmentally friendly and more suited to theenvironmental constraints which are increasingly imposed on commercialoperations. Furthermore, this process does not involve a precipitationprocess. In addition, in one process embodiment there is no necessity offorming an anionic clay as intermediate, thereby simplifying theprocess.

This process can include additional steps, for instance an intermediatedrying step, a shaping step, a milling step, an additional aging step,an additional calcination step, or washing and filtering steps.Moreover, additional compounds like acids, bases, or metal compounds canbe added where appropriate.

In the above sixth embodiment, step c) may not performed, meaning thatthe product of step b) is contacted with the ammonium transition metalsalt, i.e. step d). In this embodiment anionic clay is not formed as anintermediate, although a small amount might be formed during step a).

Step c) may be performed, whereby anionic clay is formed as intermediateproduct by rehydrating the material resulting from step b).

During aging step e), aluminium is removed from the intermediatematerial. If the material is filtered and washed after step e) and ifthe aging conditions are such that the removed aluminium does not becomeinsoluble, this aluminium will not end up in the final product. However,if no washing step is applied and/or if insoluble aluminium compoundsare formed during aging, aluminium will end up in the final compositionas a separate aluminium-containing compound, such as an aluminium oxideor hydroxide, a metal aluminate, or aluminium molybdate. As will beexplained below, the presence of this separate aluminium-containingcompound may have several advantages.

The invention, therefore, also relates to compositions comprising CLMand aluminium oxide or hydroxide, metal aluminate, or aluminiummolybdate as such.

Water-insoluble Aluminium Source

The water-insoluble aluminium source that can be used in the process ofthe invention includes aluminium oxides and hydroxides, such as gelalumina, boehmite, pseudoboehmite (either peptised or not), aluminiumtrihydrates, thermally treated aluminium trihydrates, and mixturesthereof. Examples of aluminium trihydrates are crystalline aluminiumtrihydrate (ATH), for example gibbsites provided by Reynolds AluminiumCompany RH-20® or JM Huber Micral® grades, BOC (Bauxite OreConcentrate), bayerite, and nordstrandite. BOC is the cheapestwater-insoluble aluminium source.

The water-insoluble aluminium source preferably has a small particlesize, preferably below 10 microns.

Calcined aluminium trihydrate is readily obtained by thermally treatingaluminium trihydrate (gibbsite) at a temperature ranging from about 100°to about 1,000° C. for about 15 minutes to about 24 hours. In any event,the calcining temperature and the time for obtaining calcined aluminiumtrihydrate should be sufficient to cause a measurable increase of thesurface area compared to the surface area of the gibbsite as produced bythe Bayer process, which is generally between about 30 and about 50m²/g. Within the context of this invention flash calcined alumina (e.g.Alcoa CP® alumina) is also considered to be a thermally treated form ofaluminium trihydrate. Flash calcined alumina is obtained by treatingaluminium trihydrate at temperatures between about 800° and about 1,000°C. for very short periods of time in special industrial equipment, as isdescribed in U.S. Pat. Nos. 4,051,072 and 3,222,129.

The water-insoluble aluminium source may have been doped with metalcompounds, for instance rare earth metals or transition metals. Examplesare compounds of, for instance, Ce, La, V, Mg, Ni, Mo, W, Mn, Fe, Nb,Ga, Si, P, Bi, B, Ti, Zr, Cr, Zn, Cu, Co, and combinations thereof,preferably in amounts between 1 and 40 wt %. The desired metal dependson the application of the final product. For example, forhydroprocessing applications Mo, Co, Ni, W are preferred, while for FCCapplications preference is given to V, Ce, La, Ni, Zn, Fe, Cu, W, Mo.This doped water-insoluble aluminium source can be obtained by anymethod known in the art, for instance thermal or hydrothermal treatmentof a water-insoluble aluminium source with a compound of the desiredmetal. Preferably oxides, hydroxides, and carbonates of these metals areused, but also nitrates, chlorides, sulfates, phosphates, acetates, andoxalates can be used. When a doped water-insoluble aluminium source isused as a starting material for the preparation of compositionscomprising CLM and aluminium oxide or hydroxide, doped aluminium oxideor hydroxide (in a controlled amount) will be present in the finalproduct. This may be beneficial for several applications.

Divalent Metal Source

Suitable divalent metal sources to be used in the process of theinvention are compounds containing Zn²⁺, Mn²⁺, Co²⁺, Ni²⁺, Cu²⁺, Fe²⁺,Ca²⁺, Ba²⁺, and mixtures of said compounds. Both solid divalent metalsources and soluble divalent metal sources (e.g. nitrates, chlorides,acetates, etc.) are suitable. Preferably oxides, hydroxides, carbonates,hydroxycarbonates, formates, or acetates are used. Combinations ofdivalent metal sources may be used as well.

The divalent metal source may have been doped with metals, such as Al,Ga, Cr, Fe, V, B, In, Nb, W, Mo, Ta, or mixtures thereof. This dopeddivalent metal source can be obtained by any method known in the art,for instance thermal or hydrothermal treatment of a divalent metalsource with a compound of the desired metal. Preferably oxides,hydroxides, and carbonates of these metals are used, but also nitrates,chlorides, sulfates, phosphates, acetates, and oxalates can be used.

Ammonium Transition Metal Salt

The ammonium transition metal salt is preferably selected from the groupof ammonium heptamolybdate, ammonium tungstate, ammonium vanadate,ammonium dichromate, ammonium titanate, and ammonium zirconate.Combinations of these compounds may also be used.

Process Conditions

The process can be conducted in either batch or continuous mode,optionally in a continuous multi-step operation. The process can also beconducted partly batch-wise and partly continuously.

The water-insoluble aluminium source and the divalent metal source areadded to a reactor and slurried in water. The reactor can be heated byany heating source such as a furnace, microwave, infrared sources,heating jackets (either electrical or with a heating fluid), lamps, etc.The reactor may be equipped with stirrers, baffles, etc., to ensurehomogeneous mixing of the reactants.

The aqueous suspension in the reactor can be obtained by combiningwater, the divalent metal source, and the water-insoluble aluminiumsource either per se, as slurries, or combinations thereof.Additionally, in the case of a water-soluble divalent metal source, thedivalent metal source can be added as a solution. Any sequence ofaddition can be used: the divalent metal source can be added to a slurryof the water-insoluble aluminium source, the water-insoluble aluminiumsource can be added to a slurry or solution of the divalent metalsource, or the water-insoluble aluminium source and the divalent metalsource can be added to the reactor at the same time.

Optionally, the resulting mixture and/or the separate sources arehomogenised by, for instance, milling, high shear mixing or kneading.Especially when using metal sources like oxides, hydroxides orcarbonates, it is usually advisable to mill the metal sources.Preferably, both the water-insoluble aluminium source and the divalentmetal source—if water-insoluble—are milled. Even more preferably, aslurry comprising both the water-insoluble aluminium source and thedivalent metal source is milled.

If desired, organic or inorganic acids and bases, for example forcontrol of the pH, may be fed to the reactor or added to either thedivalent metal source or the water-insoluble aluminium source beforethey are fed to the reactor. A preferred pH modifier is an ammoniumbase, because upon drying no deleterious cations remain in the product.

The use of alkali metal-containing compounds is preferably avoided, asthe presence of alkali metals is undesired for several (catalytic)applications.

Optionally, the mixture may be aged after step a). This aging can beperformed under, or close to, ambient conditions, or under thermal orhydrothermal conditions. Within the context of this descriptionhydrothermal means in the presence of water (or steam) at a temperatureabove about 100° C. at elevated pressure, e.g autogenous pressure. Theaging temperature can range from about 20°–400° C. A preferredtemperature range is about 60–175° C. Suitable atmospheres comprise CO₂,N₂, and air. The preferred atmosphere is air.

With this aging step it is possible, for instance, to convert thealuminium source into another aluminium source with improved bindingproperties. For instance, it is possible to convert aluminium trihydrateinto boehmite.

This aging preferably does not result in the formation of large amountsof anionic clay, because before step b) it is preferred that less than50 wt % is formed of the theoretically possible maximum amount ofanionic clay that could be formed from the amounts of aluminium sourceand divalent metal source present in the slurry. More preferably, lessthan about 30 wt %, more preferably less than about 20 wt %, morepreferably less than about 10 wt %, and even more preferably less thanabout 5 wt % of this amount is formed before step b). Most preferably,no anionic clay is present in the slurry before conducting step b).

The calcination according to step b) is conducted at temperaturesbetween about 175° and about 1,000° C., preferably between 200° and 800°C., more preferably between 400° and 600° C., and most about 24 hours,preferably about 1–12 hours, and most preferably about 2–6 hours. Theresulting material will be referred to as the first calcined material.

The first calcined material, after an optional milling step, may berehydrated in aqueous suspension to obtain an anionic clay. Thisrehydration can be performed at thermal or hydrothermal conditions andin the presence of dissolved metal salts, such salts including nitrates,carbonates, sulfates, oxalates of divalent (e.g. Zn, Mn, Co, Ni, Cu) ortrivalent metals (e.g. Ga, Cr, Fe, V, Mo, W).

If rehydration is performed, the obtained anionic clay is subsequentlycalcined to obtain a second calcined material. This second calcinationis performed at temperatures between about 150° and about 1,000° C.,preferably between about 200° and about 800° C., more preferably betweenabout 200° and about 600° C., and most preferably around 450° C. Thiscalcination is conducted for about 15 minutes to about 24 hours,preferably about 1–12 hours, and most preferably about 2–6 hours.

A slurry of either the first (cf. the first process embodiment) or thesecond calcined material (cf. the second process embodiment) issubsequently contacted with the ammonium transition metal salt. To thisend, a slurry of the calcined material, after an optional milling step,is added to a slurry or solution of the metal salt, or vice versa. It isalso possible to treat the slurry of the calcined material at elevatedtemperature and then add the ammonium transition metal salt per se, oras a slurry or solution. Alternatively, an ammonium transition metalsalt slurry or solution can be prepared by adding another transitionmetal compound, e.g. an oxide or hydroxide, to aqueous ammonia. Ifaqueous ammonia is present in the reactor, this slurry or solution canbe prepared in situ by feeding the transition metal compound—as a solid,solution, or slurry—to the reactor.

The slurry is aged at temperatures of about 20°–300° C., preferablyabout 60°–200° C., for about 15 minutes to about 24 hours, preferablyabout 1–12 hours, more preferably about 2–6 hours, with or withoutstirring, at ambient or elevated temperature and at atmospheric orelevated pressure. Suitable atmospheres comprise CO₂, N₂, or air. Thepreferred atmosphere is air.

During this aging step, aluminium is removed from the material asdissolved species. A washing and filtering step may optionally beperformed in order to prevent at least a portion of the aluminium frombecoming part of the resulting product. The so-formed product willcomprise predominantly CLM with an X-ray diffraction pattern analogousto that of the aforementioned CLMs obtained by Astier et al. Bypredominantly CLM is meant that the product will comprise more thanabout 50% and preferably more than about 70% CLM.

Compositions comprising CLM and an aluminium-containing compound areobtained if no washing and filtering step is performed and/or ifinsoluble aluminium compounds are formed during aging by changing theaging conditions, e.g. increasing the pH and/or the temperature. Thetypes of aluminium-containing compounds will depend on the agingconditions. Examples of such aluminium-containing compounds arealuminium oxides, hydroxides, or salts, for instance boehmite, e.g.pseudo- or microcrystalline boehmite, bayerite, amorphous oxide orhydroxide, metal aluminate, or aluminium molybdate.

An important aspect of the process resides in the presence of thisaluminium-containing compound in the final product. The amount ofaluminium-containing compound in these compositions can range from about1 to 50 wt %, and is preferably between about 5 and 50 wt %. Thealuminium-containing compound may serve as a binder, create porosity anda high surface area, and introduce acidic sites. The resultingcompositions can, therefore, be advantageously used as absorbents or ascatalyst additives or supports.

The aluminium-containing compound may be crystalline or amorphous, andhave a high (>50 m²) or low (<50 m²) surface area, depending on thepreparation conditions. For instance, aging at hydrothermal conditionswith intermediate addition of base to increase the pH can result incompositions comprising CLM and microcrystalline boehmite; whereas agingat lower temperatures and pressures can result in compositionscomprising CLM and quasi-crystalline boehmite, i.e. pseudo-boehmite.

In further embodiments the invention relates to compositions comprisingCLM and a divalent metal compound (such as oxide or hydroxide), and tocompositions comprising CLM and a transition metal compound.

Compositions comprising CLM and a divalent metal compound can beprepared using the above-described process by either starting with anexcess of divalent metal source, or leaching out some of the divalentmetal from the calcined product during aging. Examples of suchcompositions are compositions of CLM and ZnO, compositions of CLM andZn(OH)₂, and compositions of CLM, ZnO, and (pseudo)boehmite.

Compositions comprising CLM and a transition metal compound can beformed using the above-described process and taking an excess ofammonium transition metal salt.

The invention also relates to compositions comprising CLM and a compoundcontaining a divalent metal, aluminium, and/or a transition metal.Examples or such compounds are Zn—Mo complexes, zinc alumininate, zincaluminium molybdate, Zn—Al anionic clay, etc.

The CLMs or CLM-containing compositions used in accordance with thepresent invention will generally be in the form of shaped bodies. Thisshaping can be conducted either after or during the preparation of theCLM or the CLM-containing composition. For instance, in theabove-described process the slurry of water-insoluble aluminium sourceand divalent metal source of step a) can be shaped before performingcalcination step b), the anionic clay formed in step c) can be shapedbefore calcination, or the material can be shaped during aging step e)by performing this step in a kneader which might be heated.

Suitable shaping methods include spray-drying, pelletising, extrusion(optionally combined with kneading), beading, or any other conventionalshaping method used in the catalyst and absorbent fields or combinationsthereof. The amount of liquid present in the slurry used for shapingshould be adapted to the specific shaping step to be conducted. It mightbe advisable to (partially) remove the liquid used in the slurry and/oradd an additional or another liquid, and/or change the pH of theprecursor mixture to make the slurry gellable and thus suitable forshaping. Various additives commonly used in the various shaping methods,such as extrusion additives, may be added to the precursor mixture usedfor shaping. During this shaping step other components may be added tothe slurry such as zeolites, clays, silicas, aluminas, phosphates, andother catalytically active materials known in the art.

For some applications it is desirable to have additives present inand/or on the CLMs or CLM-containing compositions. Suitable additivescomprise oxides, hydroxides, borates, zirconates, aluminates, sulfides,carbonates, nitrates, phosphates, silicates, titanates, and halides ofrare earth metals (for instance Ce, La), Si, P, B, Group VI, Group VIIInoble metals (e.g. Pt, Pd), alkaline earth metals (for instance Mg, Caand Ba), and transition metals (for example W, V, Mn, Fe, Ti, Zr, Cu,Co, Ni, Zn, Mo, Sn).

Said additives can easily be deposited on the CLMs or CLM-containingcompositions. Alternatively, they can be added during theabove-described process in any of its steps. The additives can forinstance be added to the starting compounds, but can also be addedseparately in any of the slurries used in that process. Alternatively,the additives can be added just before the first or the secondcalcination step. Preferably, the slurry comprising the additive ismilled.

If desired, the CLMs or the CLM-containing compositions may be subjectedto ion-exchange. Upon ion-exchange the interlayer charge-balancingcations, i.e. NH₄ ⁺, are replaced with other cations. Examples ofsuitable cations are Na⁺, K⁺, Al³⁺, Ni²⁺, Cu²⁺, Fe²⁺, Co²⁺, Zn²⁺, othertransition metals, alkaline earth and rare earth metals, and pillaringcations such as [Al₁₃]⁷⁺ Keggin ions. In the above-described processsaid ion-exchange can be conducted before or after drying the CLM orCLM-containing composition.

The present invention is further directed to catalyst compositionscomprising CLMs and CLM-containing compositions per se, i.e independentof their preparation method. Said catalyst compositions may comprise allcomponents usually present in catalyst compositions, such as matrixand/or binder material, zeolites (e.g. faujasite, pentasil, and betazeolites), additive components, and additional phases like metal oxides,sulfides, nitrides, phosphates, silica, alumina, (swellable) clay,anionic clays, preovskites, titania, titania-alumina, zirconia, spinels,and silica-alumina. For specific purposes, such as hydroprocessing, theCLM may be pretreated, e.g. sulfided.

In FCC catalyst compositions CLMs are especially suitable as activecomponents for SO_(x) and/or NO_(x) removal, metal traps, and reductionof the N and/or S content in gasoline and diesel fuels.

CLM-containing catalyst compositions can be prepared by adding the othercatalyst components to the CLMs or CLM-containing compositions beforeshaping them to form shaped bodies. Alternatively, the catalystcomponents can be mixed in a slurry with already formed (andsubsequently milled) shaped bodies of CLMs or CLM-containingcompositions. The resulting mixture can then be shaped again.

The CLMs and the CLM-containing compositions can also be combined withcatalysts as additive compositions; as such or as shaped bodies.Therefore, the present invention is also directed to catalyst additivecompositions comprising CLM. These additive compositions are especiallysuitable in FCC processes as active components for SO_(x) and/or NO_(x)removal, metal traps, and reduction of the N and/or S content ingasoline and diesel fuels, especially when metals such as Ce and/or Vare present in or on the CLM.

The CLMs and CLM-containing compositions can be further calcined to formmetal oxide compositions. Such a calcination can be performed attemperatures of about 200°–1,000° C., preferably about 400–600° C., andmore preferably close to about 450° C.

The metal oxide composition can be sulfided, reduced by hydrogen, CO, orother reducing agents, or otherwise treated to create an active catalystcomposition which can suitably be used as a catalyst or catalystadditive for FCC, HPC, dehydrogenation, and Fisher-Tropsch processes.Sulfiding, for instance, is performed by contacting the metal oxide witha sulfur bearing compound, e.g. H₂S. The sulfur bearing compound can bepassed over the metal oxide composition as a gas, or it can be presentin a slurry comprising the metal oxide composition.

Alternatively, the metal oxide composition can be rehydrated in aqueoussolution and optionally in the presence of additives to form a CLM orCLM-containing composition, optionally containing an additive.

EXAMPLES Example 1

A mixture of 15.3 g gibbsite and basic zinc carbonate, ZnCO₃.2ZnO.H₂O,(Zn/Al atomic ratio of 3:1) was slurried in 130 ml of water. The slurrywas milled. The resulting slurry was dried and subsequently calcined at500° C. for 4 hours. The material (10 g) was then heated to 85° C. andaged overnight, while stirring in an aqueous solution (550 ml) of 0.042M ammonium heptamolybdate. The product was filtered and washed.According to the powder X-ray diffraction pattern, the product containeda cationic layered material structurally identical to that reported byM. P. Astier et al.

Elemental analysis using SEM-EDAX showed the Zn/Al molar ratio in theproduct to be 1.25. Hence, the product was a composition comprising CLMand an aluminium-containing compound.

Example 2

Zn-doped pseudoboehmite was prepared by treating flash calcined gibbsite(42.5 g) for 2 hours in an aqueous solution of zinc nitrate (10 wt. %Zn²⁺) at 120° C., pH 4 (pH adjustment with HNO₃). The solids content ofthe slurry was 20 wt %. This Zn-doped pseudoboehmite (172 g) was thenmixed with basic zinc carbonate (sufficient for reaching a Zn/Al atomicratio of 2), slurried in water (final solids content 22%), and milled.The slurry was dried and subsequently calcined at 500° C. for 4 hours.The calcined product (10 g) was aged overnight, while stirring in 550 mlof a 0.092 M solution of ammonium heptamolybdate at 85° C. The resultingmaterial was filtered, washed, and dried at 85° C. overnight. Accordingto the powder X-ray diffraction pattern, the product contained acationic layered material structurally identical to that reported by M.P. Astier et al.

Example 3

A mixture of 15.3 g gibbsite, basic nickel carbonate, and zinc hydroxycarbonate was slurried in 285 ml of water. The atomic ratio (Zn+Ni):Alwas 3:1, whereas the Ni:Zn ratio was 1:1. The slurry was milled. Theresulting slurry was dried and subsequently calcined at 500° C. for 4hours. The calcined material (10 g) was then heated to 85° C. and agedovernight, while stirring in an aqueous solution (550 ml) of 0.042 Mammonium heptamolybdate. The product was filtered and washed. Accordingto the powder X-ray diffraction pattern, the product contained acationic layered material structurally identical to that reported by M.P. Astier et al.

Example 4

A mixture of 21.3 g Chattem™ amorphous gel alumina and 11.8 g basic zinccarbonate (Zn:Al atomic ratio 3.0) was slurried in water (solids content19 wt %) and subsequently calcined at 500° C. for 4 hours in air in amuffle furnace. Of the resulting product, 62.9 g was rehydrated in 1657ml 1M sodium carbonate at 70° C. for 3 days while stirring. The PXRDpattern confirmed the formation of a Zn—Al anionic clay with a smallamount of ZnO.

The so-prepared Zn—Al anionic clay was calcined at 400° C. for 4 hoursin air. The calcined product (10 g) was slurried in 550 ml of a 0.042 Mammonium heptamolybdate solution while stirring. The mixture was heatedand then mixed with the calcined Zn—Al anionic clay. The resultingslurry was left under stirring overnight at 85° C. and was subsequentlyfiltered, washed with de-ionised water, and dried overnight at 100° C.According to the powder X-ray diffraction pattern, the product containeda cationic layered material structurally identical to that reported byM. P. Astier et al.

Example 5

A mixture of 15.3 g gibbsite and basic copper carbonate (Cu:Al atomicratio of 3:1) was slurried in 140 ml of water. The slurry was milled.The resulting slurry was dried and subsequently calcined at 550° C. for4 hours. The calcined material then heated to 85° C. and aged overnight,while stirring in an aqueous solution (550 ml) of 0.042 M ammoniumheptamolybdate. The product was filtered and washed. According to thepowder X-ray diffraction pattern, the product contained a cationiclayered material structurally identical to that reported by M. P. Astieret al.

Elemental analysis using SEM-EDAX showed the overall Cu/Al molar ratioin the bulk of the product to be 2. Hence, the product was a compositioncomprising CLM and an aluminium-containing compound.

Example 6

A mixture of 10.6 g flash calcined gibbsite (Alcoa CP® alumina) and 73.7g basic zinc carbonate (Zn:Al ratio of 3:1) was slurried in water(solids content 18.3 wt %). The resulting slurry was dried at 100° C.and subsequently calcined at 300° C. for 4 hours in air in a mufflefurnace. Of the resulting product, 55.4 g was rehydrated in 2770 ml 1 Msodium carbonate at 70° C. for 3 days while stirring. The product wasfiltered, washed and dried at 100° C. The PXRD pattern confirmed theformation of a Zn—Al anionic clay with a small amount of ZnO.

The so-prepared Zn—Al anionic clay was calcined at 500° C. for 3 hoursin air. To 15.0 g or the calcined product was added 150 ml of a 0.3 Mammonium heptamolybdate solution. The mixture was heated to 85° C. andaged overnight. The product was filtered and washed with de-ionisedwater, and dried overnight at 100° C. According to the powder X-raydiffraction pattern, the product contained a cationic layered materialstructurally identical to that reported by M. P. Astier et al.

Example 7

A mixture of 22.9 g gibbsite and basic zinc carbonate (Zn:Al ratio of3:1) was slurried in 335 ml of water. The slurry was milled. Theresulting slurry was dried and subsequently calcined at 500° C. for 4hours. After calcination, the product was rehydrated in a 1M Na₂CO₃solution at 65° C. for 8 hours. This anionic clay was calcined at 400°C. for 4 hours.

The calcined product (10 g) was then aged overnight at room temperature,while stirring in an aqueous solution (550 ml) of 0.042 M ammoniumheptamolybdate. The product was directly dried at 100° C. According tothe powder X-ray diffraction pattern, the product contained a cationiclayered material structurally identical to that reported by M. P. Astieret al.

Example 8

A mixture of 15.3 g gibbsite and basic zinc carbonate, ZnCO₃.2ZnO.H₂O,(Zn/Al atomic ratio of 3:1) and 12 wt % cerium nitrate—calculated asCeO₂ and based on total dry product weight—was slurried in 250 ml ofwater. The slurry was milled. The resulting slurry was dried andsubsequently calcined at 500° C. for 4 hours. The material (10 g) wasthen heated to 85° C. and aged overnight, while stirring in an aqueoussolution (550 ml) of 0.042 M ammonium heptamolybdate. The product wasfiltered, washed with de-ionised water, and dried overnight at 100° C.

The resulting product was a Ce-containing cationic layered material.

Example 9

A mixture of 15.3 g gibbsite and basic zinc carbonate, ZnCO₃.2ZnO.H₂O,(Zn/Al atomic ratio of 3:1) and 4 wt % ammonium metavanadate—calculatedas V₂O₅ and based on total dry product weight—(from; the % based ontotal dry weight of Al₂O₃ and ZnO) was slurried in 250 ml of water. Theslurry was milled. The resulting slurry was dried and subsequentlycalcined at 500° C. for 4 hours. The material (10 g) was then heated to85° C. and aged overnight, while stirring in an aqueous solution (550ml) of 0.042 M ammonium heptamolybdate. The product was filtered, washedwith de-ionised water, and dried overnight at 100° C.

The resulting product was a V-containing cationic layered material.

Example 10

A mixture of 15.3 g gibbsit, basic zinc carbonate, ZnCO₃.2ZnO.H₂O,(Zn/Al atomic ratio of 3:1), 12 wt % cerium nitrate, and 4 wt % ammoniummetavanadate—both calculated as oxides and based on total dry productweight—was slurried in 300 ml of water. The slurry was milled. Theresulting slurry was dried and subsequently calcined at 500° C. for 4hours. The material (10 g) was then heated to 85° C. and aged overnight,while stirring in an aqueous solution (550 ml) of 0.042 M ammoniumheptamolybdate. The product was filtered, washed with de-ionised water,and dried overnight at 100° C.

The resulting product was a Ce and V-containing cationic layeredmaterial.

Example 11

A mixture of 15.3 g gibbsite and basic zinc carbonate, ZnCO₃.2ZnO.H₂O,(Zn/Al atomic ratio of 3:1) was slurried in 130 ml of water. The slurrywas milled. The resulting slurry was dried and subsequently calcined at500° C. for 4 hours. The material (10 g) was then heated to 85° C. andaged overnight, while stirring in an aqueous solution (550 ml) of 0.042M ammonium heptamolybdate. The product was filtered, washed withde-ionised water, and dried overnight at 100° C. This product wasslurried in a 150 ml solution containing 12 wt % ceriumnitrate—calculated as CeO₂ and based on dry product weight. Theresulting slurry was dried at 100° C.

The final product was a cerium-impregnated CLM.

Example 12

A mixture of 15.3 g gibbsite and basic zinc carbonate, ZnCO₃.2ZnO.H₂O,(Zn/Al atomic ratio of 3:1) was slurried in 130 ml of water. The slurrywas milled. The resulting slurry was dried and subsequently calcined at500° C. for 4 hours. The material (10 g) was then heated to 85° C. andaged overnight, while stirring in an aqueous solution (550 ml) of 0.042M ammonium heptamolybdate. The product was filtered, washed withde-ionised water, and dried overnight at 100° C. This product wasslurried in 150 ml of a solution containing 4 wt % ammoniummetavanadate—calculated as V₂O₅ and based dry product weight. Theresulting slurry was dried at 100° C.

The final product was a vanadium-impregnated CLM.

Example 13

A mixture of 15.3 g gibbsite and basic zinc carbonate, ZnCO₃.2ZnO.H₂O,(Zn/Al atomic ratio of 3:1) was slurried in 130 ml of water. The slurrywas milled. The resulting slurry was dried and subsequently calcined at500° C. for 4 hours. The material (10 g) was then heated to 85° C. andaged overnight, while stirring in an aqueous solution (550 ml) of 0.042M ammonium heptamolybdate. The product was filtered, washed withde-ionised water, and dried overnight at 100° C. This product wasslurried in a 150 ml solution containing 12 wt % cerium nitrate and 150ml of a solution containing 4 wt % ammonium metavanadate—both calculatedas oxides and based on dry product weight. The resulting slurry wasdried at 100° C.

The final product was a cerium and vanadium-impregnated CLM.

Example 14

A mixture of 19.9 g gibbsite, basic nickel carbonate, and zinc hydroxycarbonate was slurried in 200 ml of water. The ratio (Zn+Ni):Al ratio of3:1, whereas the Ni:Zn ratio was 3:7. The slurry was milled. Theresulting slurry was dried and subsequently calcined at 550° C. for 4hours. The calcined product (10.0 g) was heated to 85° C. and agedovernight, while stirring in an aqueous solution (550 ml) of 0.042 Mammonium heptamolybdate. The product was filtered and washed.

According to the powder X-ray diffraction pattern, the product containeda cationic layered material structurally identical to that reported byM. P. Astier et al. Elemental analysis using SEM-EDAX showed thepresence of aluminium compounds in the product.

Example 15

A mixture of 15.3 g gibbsite, basic copper basic carbonate, and zinchydroxy carbonate was slurried in 285 ml of water. The atomic ratio(Zn+Cu):Al was 3:1, whereas the Zn:Cu ratio was 1:1. The slurry wasmilled. The resulting slurry was dried and subsequently calcined at 500°C. for 4 hours. The calcined material (15 g) was then heated to 85° C.and aged overnight, while stirring in an aqueous solution (150 ml) of0.3 M ammonium heptamolybdate. The product was filtered, washed withde-ionised water, and dried overnight at 100° C. According to the powderX-ray diffraction pattern, the product contained a cationic layeredmaterial structurally identical to that reported by M. P. Astier et al.

Example 16

A mixture of 2.0 g gibbsite and basic zinc carbonate, ZnCO₃.2ZnO.H₂O,(Zn/Al atomic ratio of 10:1) was slurried in 160 ml of water. The slurrywas milled. The resulting slurry was dried and subsequently calcined at500° C. for 4 hours. The material (15 g) was then heated to 85° C. andaged overnight, while stirring in an aqueous solution (150 ml) of 0.3 Mammonium heptamolybdate. The product was filtered, washed withde-ionised water, and dried overnight at 100° C. According to the powderX-ray diffraction pattern, the product contained a cationic layeredmaterial structurally identical to that reported by M. P. Astier et al.

Example 17

The products of Examples 1, 2, 7, and 14 were tested for their de-SOxability in FCC processes using the thermographimetric test described inInd. Eng. Chem. Res. Vol. 27 (1988) pp. 1356–1360. A standard commercialde-SOx additive (REF) was used as a reference.

30 mg of the product sample was heated under nitrogen at 700° C. for 30minutes. Next, the nitrogen was replaced by a gas containing 0.32% SO₂,2.0% O₂, and balance N₂ with a flow rate of 200 ml/min. After 30 minutesthe SO₂-containing gas was replaced by nitrogen and the temperature wasreduced to 650° C. After 15 minutes, nitrogen was replaced by pure H₂and this condition was maintained for 20 minutes. This cycle wasrepeated 3 times. The sample's SO_(x) uptake and its release duringhydrogen treatment were measured as the sample's weight change (in %).

The SOx uptake and release during the third cycle are shown in Table I.This Table also displays the effectiveness ratio, which is defined asthe ratio of SO_(x) release over SO_(x) uptake. The ideal effectivenessratio is 1, which means that all the SO_(x) that was taken up has beenreleased again, leading to a longer catalyst life.

TABLE I SOx uptake SOx release Effectiveness Sample (% weight increase)(% weight decrease) ratio Example 1 3.06 2.37 0.77 Example 2 2.75 2.000.73 Example 7 2.09 1.04 0.50 Example 4.46 3.69 0.83 14 REF 4.89 1.510.31This table shows that the effectiveness ratios of the samples accordingto the invention are higher than that of a standard commercial de-SOxadditive.

Example 18

The products of Examples 1, 2, 15, and 16 were tested for their abilityto reduce the sulfur content of FCC gasoline.

The samples to be tested were calcined for 2 hours. The calcined sampleswere blended with a commercial FCC catalyst; the blend containing 20 wt% of the desired sample and 80 wt % of FCC catalyst.

The blends were tested in a fixed bed test unit (MST) using a regularFCC feed containing 2.9 wt % of sulfur and a cracking temperature of550° C. The sulfur content of the gasoline was measured at threedifferent catalyst to oil ratios: 2.5, 3.5, and 4.5.

Two reference samples were tested:

-   Sample ref A: 100% of a standard E-cat-   Sample ref B: a blend containing 20 wt % of a commercial FCC    additive for the reduction of S in gaoline.

FIG. 1 displays the S content of the gasoline versus the conversion forthe tested samples at the three catalyst to oil ratios. It is clear thatcationic layered materials are able to reduce the sulfur content ofgasoline.

Example 19

The products of Examples 3, 5, 7, and 15 were tested for their de-NOxability in FCC processes. These samples showed good de-NOx properties.

1. A process for the preparation of a cationic layered material from an aluminium source and a divalent metal source, comprising the steps of: a) preparing a slurry comprising a water-insoluble aluminium source and a divalent metal source, b) drying the slurry of step a) and calcining the dried material to form a first calcined material, c) optionally rehydrating the product of step b) to obtain an anionic clay, followed by calcining the anionic clay to form a second calcined material, d) contacting a slurry of either the first or the second calcined material with an ammonium transition metal salt, and e) aging the resulting slurry.
 2. The process of claim 1 wherein the slurry of step a) is aged before conducting step b).
 3. A process of claim 1 wherein the product of step e) is filtered and washed.
 4. The process of claim 1 wherein in step b) the dried slurry is shaped before calcination.
 5. The process of claim 1 wherein the anionic clay obtained in step c) is shaped before calcination.
 6. The process of claim 1 wherein the water-insoluble aluminium source is selected from the group consisting of alumina gel, boehmite, pseudoboehmite, aluminium trihydrate, thermally treated forms of aluminium trihydrate, and mixtures thereof.
 7. The process of claim 1 wherein the water-insoluble aluminium source is doped with at least one metal compound.
 8. The process of claim 1 wherein the divalent metal is an oxide, hydroxide, hydroxycarbonate, carbonate, formate, or acetate of Zn²⁺, Mn²⁺, Co²⁺, Ni²⁺, Fe²⁺ or Cu²⁺, or a combination thereof.
 9. The process of claim 1 wherein the ammonium transition metal salt is an ammonium transition metal salt selected from the group consisting of ammonium heptamolybdate, ammonium tungstate, ammonium vanadate or ammonium dichromate, and combinations thereof.
 10. The process of claim 1 wherein the product of step e) is dried and the resulting dried product is calcined at about 200–1,000° C.
 11. The process of claim 10 wherein the calcined product is rehydrated in the presence of an additive.
 12. A composition comprising a cationic layered material and a divalent metal compound prepared by the process of claim
 1. 13. The composition of claim 12 containing one or more additives selected from the group consisting of oxides, hydroxides, borates, zirconates, aluminates, sulfides, carbonates, nitrates, phosphates, silicates, titanates, molybdates, tungstates and halides of rare earth metals Si, P, B, Group VI metals, Group VIII noble metals, alkaline earth metals and transition metals.
 14. An FCC catalyst composition comprising the cationic layered material of claim
 12. 15. An FCC catalyst additive composition comprising the cationic layered material of claim
 12. 16. The composition of claim 12 and a transition metal compound.
 17. The composition of claim 12 and compounds of one or more of aluminum, chromium or iron.
 18. A process for the conversion, purification, or synthesis of hydrocarbons wherein hydrocarbons are contacted with a cationic layered material as claimed in claim 12 at hydrocarbon conversion, purification, or synthesis conditions.
 19. The process of claim 18 wherein the process is a hydrodesulfurization, hydrodenitrogenation, fluid catalytic cracking, or Fischer-Tropsch process.
 20. The process of claim 19 wherein the process is a fluid catalytic cracking process for the reduction of the nitrogen and/or sulfur content of fuels.
 21. The process of claim 20 wherein said fuels comprise gasoline and/or diesel.
 22. The process of claim 18 wherein the process effects reduction of SOx and/or NOx emissions.
 23. A composition comprising a cationic layered material prepared by the process of claim 1 comprising about 1–50 weight percent of aluminium oxide, aluminium hydroxide, metal aluminate, or aluminium molybdate in said composition.
 24. The composition of claim 23 wherein the aluminium oxide or hydroxide is doped with rare earth metals or transition metals.
 25. The composition of claim 23 containing one or more additives selected from the group consisting of oxides, hydroxides, borates, zirconates, aluminates, sulfides, carbonates, nitrates, phosphates, silicates, titanates, molybdates, tungstates and halides of rare earth metals Si, P, B, Group VI metals, Group VIII noble metals, alkaline earth metals and transition metals.
 26. An FCC catalyst composition comprising the cationic layered material of claim
 23. 27. An FCC catalyst additive composition comprising the cationic layered material of claim
 23. 28. The composition of claim 23 and a transition metal compound.
 29. A hydroprocessing catalyst comprising the composition prepared by the process of claim
 1. 30. A Fischer-Tropsch catalyst comprising the composition prepared by the process of claim
 1. 31. The composition prepared by the process of claim 1 and compounds of one or more of aluminum, chromium or iron.
 32. A shaped body obtained by the process of claim
 4. 33. A shaped body obtained by the process of claim
 5. 